A unique ultrarefractory inclusion from the Murchison meteorite

Abstract— Through freeze-thaw disaggregation of the Murchison meteorite, we have recovered a refractory inclusion, HIB-11, that is unique in terms of its texture, mineral compositions, and bulk composition. It consists of anhedral, Y-rich (1.6 wt% Y₂O₃) perovskite and lathlike spinel grains enclosed in a matrix of fine-grained, Sc-rich (10.5 wt% SC₂O₃ avg.), Ti-rich (12.6 wt% TiO₂ avg., reporting all Ti as TiO₂) clinopyroxene. The chondrite-normalized rare earth element (REE) pattern is complex, with light REE (LREE) at ～10× C1, abundances increasing from Gd through Ho (the latter at ～10⁴× C1), decreasing through Yb at 200× C1, and Lu at ～400× C1. The pattern reflects several stages of high-temperature volatility fractionation. Removal of Lu and Er from the source gas in the first condensation event was followed by partial to complete removal of the somewhat less refractory heavy REE, Gd through Ho, in the HIB-11 precursors by condensation from the fractionated residual gas in a second event. Both of these events probably reflect condensation of REE into ZrO₂ or a mixed Zr-, Sc-, Ti-, Y-oxide at temperatures too high for hibonite stability. A second, lower-temperature component, which was subsequently added, had fractionated (Nd-poor, Ce-rich) LREE abundances that resulted from condensation from a gas that had undergone prior removal of the more refractory LREE, resulting in enrichment in Ce and the most volatile REE, Eu and Yb. The aggregate was then melted and quickly cooled, forming a fine-grained spherule. This is the first reported inclusion in which the two most refractory REE, Lu and Er, are strongly fractionated from the other REE. An absence of mass fractionation among the Ti isotopes indicates that HIB-11 is not an evaporative residue, implying that volatility fractionation of trace elements took place during condensation. The fact that the two most refractory heavy REE could be separated from the other, only slightly less refractory heavy REE suggests that a wide variety of REE patterns is possible, and that ultrarefractory inclusions with other unusual REE patterns, important recorders of nebular condensation, may yet be discovered.     

Models of the millimeter-centimeter spectra of the giant planets

Hitherto Jupiter's spectrum at short millimeter wavelenghts showed a clear discrepancy with model calculations (e.g., G.L. Berge and S. Gulkis, 1976, In Jupiter (T. Gehrels, Ed.), pp. 621–692. Univ. of Arizona Press, Tucson). A similar although less pronounced, discrepancy appears to exist for Uranus and Neptune. One explanation of this discrepancy is that additional absorbers not included in the model calculations are present in the atmosphere. It was suggested that uncertainties in the absorption coefficient of ammonia, especially at millimeter wavelengths, may be responsible for at least part of the discrepancy. A comparison of various model atmosphere calculations with data for all four giant planets is shown. The absorption profile of ammonia at centimeter wavelengths was assumed to be rightly represented by a Ben Reuven line profile, which enabled the derivation of information on the vertical distribution of ammonia in these planets' atmospheres. It appeared that ammonia must be depleted in the upper atmospheres of all four planets by a factor of 4–5 with respect to the solar abundance for Jupiter (and Saturn) and by a factor of 100–200 for Uranus and Neptune. At deeper layers the optical depth is larger, due either to a larger abundance of ammonia or to absorption by the presence of water. Given the vertical ammonia distribution in the atmospheres as derived from the centimeter data, a best fit to the millimeter spectra of all four planets was found by changing the high frequency tail of the ammonium lineshape profile. This, we feel, is legitimate since the profile at millimeter wavelenghts is not or is only poorly known due to the absence of laboratory spectra for ammonia as a trace constituent in an otherwise hydrogen gas. It was found that a line profile which at millimeter wavelenghts more closely resembles a Van Vleck-Weisskopf lineshape than the usually adopted Ben Reuven profile gives a rather satisfactory fit to the data of all four gaseous planets.     

Patterns of Plant Diversity in Georgia and Texas Salt Marshes

A fundamental question in ecology is how biological interactions and biogeographic processes interact to determine the biodiversity of local sites. We quantified patterns of plant species diversity on transects across elevation at 59 salt marsh sites in Georgia and 49 sites in Texas. Although these regions have similar climates and floras, we anticipated that diversity might differ because of differences in tidal regime. Diversity was measured at global, regional, site, and plot scales to consider processes occurring at all levels. Species pools were similar between regions. Texas had greater diversity at the site and plot scales, suggesting that processes occurring at the site scale differed. The greater diversity of Texas sites and plots was associated with wider distributions of individual species across the marsh landscape and proportionally more middle marsh (a high diversity zone) and less low marsh (a low diversity zone) than in Georgia marshes. Preliminary data suggested that these differences were not due to differences in salinity regime or standing biomass between regions, leaving differences in tidal regime as the most plausible hypothesis accounting for differences in plant diversity. We speculate that the less-predictable tidal regime in Texas leads to temporal variation in abiotic conditions that limit the ability of any one species to competitively exclude others from particular marsh zones.     

Influences of the unsaturated,saturated, and riparian zones on the transport of nitrate near the Merced River,California, USA

Transport and transformation of nitrate was evaluated along a 1-km groundwater transect from an almond orchard to the Merced River, California, USA, within an irrigated agricultural setting. As indicated by measurements of pore-water nitrate and modeling using the root zone water quality model, about 63% of the applied nitrogen was transported through a 6.5-m unsaturated zone. Transport times from recharge locations to the edge of a riparian zone ranged from approximately 6 months to greater than 100 years. This allowed for partial denitrification in horizons having mildly reducing conditions, and essentially no denitrification in horizons with oxidizing conditions. Transport times across a 50–100-m-wide riparian zone of less than a year to over 6 years and more strongly reducing conditions resulted in greater rates of denitrification. Isotopic measurements and concentrations of excess N₂ in water were indicative of denitrification with the highest rates below the Merced River. Discharge of water and nitrate into the river was dependent on gradients driven by irrigation or river stage. The results suggest that the assimilative capacity for nitrate of the groundwater system, and particularly the riverbed, is limiting the nitrate load to the Merced River in the study area.     

Spinifex biogeochemical expressions of buried gold mineralisation: The great mineral exploration penetrator of transported regolith

A major challenge for mineral explorers is to efficiently detect mineralisation beneath the weathered cover that extends across the landscape. Determination of the elemental composition of plants (biogeochemical exploration) can aid in the detection of buried ore deposits due to their root penetration through the weathered cover. At the coyote prospect in Western Australia a range of plant species were sampled traversing a buried Au orebody. Here it is shown that the soft spinifex (Triodia pungens) accumulated important pathfinder elements related to the mineralisation, which produced a multi-element surficial expression of the underlying ore deposit. Spinifex grasses are one of the most widespread grasses over the Australian continent and have vertical root systems that can extend for many 10s of metres through sedimentary cover and interact with buried mineral deposits and alteration zones in the underlying substrate. Spinifex biogeochemistry therefore has potential to be a low cost, low environmental impact, sampling medium for mineral exploration programs across large parts of arid Australia. The examination of similar grasses from other semi-arid and arid regions from around the world therefore also warrants further investigation.     

Contamination,risk, and heterogeneity: on the effectiveness of aquifer remediation

The effectiveness of aquifer remediation is typically expressed in terms of a reduction in contaminant concentrations relative to a regulated maximum contaminant level (MCL), and is usually confirmed by sparse monitoring data and/or simple model calculations. Here, the effectiveness of remediation is re-examined from a more thorough risk-based perspective that goes beyond the traditional MCL concept. A methodology is employed to evaluate the health risk to individuals exposed to contaminated household water that is produced from groundwater. This approach explicitly accounts for differences in risk arising from variability in individual physiology and water use, the uncertainty in estimating chemical carcinogenesis for different individuals, and the uncertainties and variability in contaminant concentrations within groundwater as affected by transport through heterogeneous geologic media. A hypothetical contamination scenario is developed as a case study in a saturated, alluvial aquifer underlying an actual Superfund site. A baseline (unremediated) human exposure and health risk scenario, as induced by contaminated groundwater pumped from this site, is predicted and compared with a similar estimate based upon pump-and-treat exposure intervention. The predicted reduction in risk in the remediation scenario is not an equitable one—that is, it is not uniform to all individuals within a population and varies according to the level of uncertainty in prediction. The importance of understanding the detailed hydrogeologic connections that are established in the heterogeneous geologic regime between the contaminated source, municipal receptors, and remediation wells, and its relationship to this uncertainty is demonstrated. Using two alternative pumping rates, we develop cost-benefit curves based upon reduced exposure and risk to different individuals within the population, under the presence of uncertainty.     

Quantification of co-occurring reaction rates in deep subseafloor sediments

Net rates of biogeochemical reactions in subseafloor sediments can be quantified from concentration profiles of dissolved reactants or products and physical properties of the sediment. To study net rates of microbial activities in deep sediments, we developed a robust approach that is well suited to use over a broad range of sediment depths. Our approach is based on a finite-difference solution to a continuity equation that considers molecular diffusion, sediment burial, fluid advection, and reaction under the assumption of steady state. Numerical procedures are adopted to identify the maximum number of depth intervals with statistically different reaction rates. The approach explicitly considers downcore variation in physical properties and sample spacing. Uncertainties in the rate estimates are quantified using a Monte Carlo technique. We tested our approach using synthetic concentration profiles generated from analytical solutions to the continuity equation. We then applied the approach to concentration profiles of dissolved sulfate, sulfide, methane, and manganese in the 420-m thick sediment column of eastern equatorial Pacific Ocean Drilling Program Site 1226. Our results indicate that (i) sulfate reduction and iron reduction occur at most sediment depths, (ii) net methane production occurs in discrete depth intervals and (iii) manganese reduction occurs near the seafloor and deep in the sediments. These results provide quantitative evidence that multiple respiration pathways co-exist in the same depth intervals of these deep subseafloor sediments.     

Geochemical fluxes and weathering of volcanic terrains on high standing islands: Taranaki and Manawatu-Wanganui regions of New Zealand

Sediment fluxes from high standing oceanic islands (HSIs) such as New Zealand are some of the highest known [Milliman J. D. and Syvitski J. P. M. (1992) Geomorphic/tectonic control of sediment discharge to the ocean: the importance of small mountainous rivers. J. Geol.100, 525-544]. Recent geochemical work has suggested that along with their extremely high physical weathering yields, many New Zealand watersheds also have very high chemical weathering yields. In New Zealand, the magnitude of both the physical and chemical weathering yields is related to the lithology of the watershed. Most of the previous work on this topic has been undertaken in Southern Alps watersheds of schist and greywacke and in East Cape watersheds of semi-consolidated marine sediments and greywacke. We recently sampled North Island watersheds in the Taranaki and Manawatu-Wanganui regions which have been subjected to volcanism since the Miocene. We sampled watersheds that contain both volcanic and sedimentary rocks. A series of water and sediment samples was collected and analyzed for major, minor and trace elements. This was done to quantify the weathering intensities in the watersheds and to establish the relationship between physical and chemical weathering yields in volcanic lithologies. Our results reveal distinct chemical signatures for the different regions. Waters draining the Taranaki region volcanics are significantly enriched in K⁺, and depleted in Ca²⁺ and Sr²⁺ compared to waters draining the Manawatu-Wanganui region volcanics, which also traverse expanses of sedimentary siltstones and mudstones. The Ca²⁺ and Sr²⁺ depletions may reflect the relative absence of CaCO₃ in the Taranaki region watersheds. In addition, sediment samples from the Taranaki region show significant enrichment in Ti, Al, Ca, Fe, Mn, Mg, Ca, and P and depletion in Si and Rb compared to those of the Manawatu-Wanganui region. From total dissolved solids concentrations and mean annual water discharge, we calculate chemical weathering yields of 60-240 tons km⁻² a⁻¹. These weathering yields fall within the middle to upper range of those previously documented for the Southern Alps (93-480 tons km⁻² a⁻¹) and East Cape (62-400 tons km⁻² a⁻¹). Calculated silicate weathering yields of 12-33.6 tons km⁻² a⁻¹ and CO₂ consumption of 852-2390 × 10³ mol km⁻² a⁻¹ for the rivers draining the Taranaki volcanic region are higher than those previously reported for watersheds hosted in sedimentary and metamorphosed rock terrains on HSIs. CO₂ consumption is found to be within the range previously measured for the basaltic terrains of the Deccan Traps (580-2450 × 10³ mol km⁻² a⁻¹) and Réunion Island(1300-4400 × 10³ mol km⁻² a⁻¹). Our calculated chemical weathering yields demonstrate the importance of HSIs, particularly those with volcanic terrains, when considering global geochemical fluxes.